EP1299495A2 - Adhesifs a performance amelioree en decoupage a la presse - Google Patents

Adhesifs a performance amelioree en decoupage a la presse

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Publication number
EP1299495A2
EP1299495A2 EP01950605A EP01950605A EP1299495A2 EP 1299495 A2 EP1299495 A2 EP 1299495A2 EP 01950605 A EP01950605 A EP 01950605A EP 01950605 A EP01950605 A EP 01950605A EP 1299495 A2 EP1299495 A2 EP 1299495A2
Authority
EP
European Patent Office
Prior art keywords
diblock
styrene
copolymer
adhesive
adhesive according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP01950605A
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German (de)
English (en)
Other versions
EP1299495B1 (fr
Inventor
Jacques B. Lechat
Olivier J. Georjon
Francois-X. Gibert
Gerard Marin
Michael Oliver Myers
Roger R. Delme
Kenneth Lewtas
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dow Chemical Co
Original Assignee
ExxonMobil Chemical Patents Inc
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Filing date
Publication date
Application filed by ExxonMobil Chemical Patents Inc filed Critical ExxonMobil Chemical Patents Inc
Priority to EP08000424A priority Critical patent/EP1905808B1/fr
Publication of EP1299495A2 publication Critical patent/EP1299495A2/fr
Application granted granted Critical
Publication of EP1299495B1 publication Critical patent/EP1299495B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/387—Block-copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/24—Graft or block copolymers according to groups C08L51/00, C08L53/00 or C08L55/02; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

Definitions

  • the present invention is directed to elastomer or rubber based pressure-sensitive adhesive compositions particularly useful in label and tape manufacture.
  • a laminate of a face stock, a pressure-sensitive adhesive layer, and a release liner, such as silicone-coated paper is passed tlirough an apparatus that converts the laminate into commercially useful labels and label stock.
  • the converting operation processes involve printing, die-cutting, and matrix stripping to leave labels on a release liner, marginal hole punching, perforating, fan folding, guillotining and the like. It is important that the cutting action breaks the face stock and adhesive layer, but does not indent the release liner.
  • Producing a series of labels on a backing sheet involves cutting around the label and removing the material between two labels (the matrix) while leaving the label itself attached to the backing sheet.
  • Adhesives for these applications are formulated to have suitable viscoelastic and adhesive properties so that they can be applied to the release liner or face-stock back and will remain on the label after stripping with the required adhesion. But these properties make the adhesive film difficult to cut or break. They make die cutting difficult and inconsistent, and cause adhesive strings and deposits on the cutting blade.
  • Die cutting involves cutting the laminate through to the release liner face. Other procedures involve cutting completely through the label laminate and include hole punching, perforating, and guillotining, particularly on flat sheets.
  • the cost of converting a laminate into a finished product, such as a label is a function of the various processing operations' rates.
  • Line speed depends on whether a printing step is involved. With no printing step, e.g. computer labels, speeds can reach 300 meters/minute. Otherwise, speeds of 50 — 100 meters/minute are typical.
  • the adhesive layer can limit convertibility ease.
  • the adhesive layer's viscoelastic nature causes this limitation - its high elasticity prevents it from flowing away from the cut line during die-cutting and also promotes its transfer to cutting blades during cutting. High adhesive elasticity also causes adhesive stringiness, which hinders matrix stripping. High elasticity also promotes adhesive layer reconnection after the layer is severed.
  • Adhesives must be formulated to fit needs. Important adhesive requirements include peel adhesion, tack, shear, and viscosity at various temperatures and on various substrates such as polymers, papers, glasses, and steels. Good, general-purpose adhesives may exhibit poor convertibility simply because the adhesive is difficult to cleanly sever. The adhesive may stick to a die or blade. Furthermore, within a speed range, use of a particular adhesive may result in breaking the matrix despite the fact that successful matrix stripping can occur at speeds on either side of the breaking speed. One goal is to provide adhesive systems where the adhesive has good die- cutting performance and where the matrix can be successfully stripped over the entire operating speed range.
  • Typical label adhesives are produced from acrylic polymer emulsions, which may be tackified by hydrocarbon- or natural-resin tackifiers. While these have good die-cutting performance, they require handling large volumes of liquid and subsequent liquid removal. At low temperature, acrylic-based adhesives perform poorer than hot-melt systems. Accordingly, hot melt adhesives would be preferred. Moreover, hot melts can be used at faster line application speeds over broader temperature ranges, can have more aggressive tack, and can be used under humid conditions.
  • Hot-melt pressure-sensitive adhesive systems consist of tackified thermoplastic elastomers such as styrenic block copolymers.
  • styrenic block copolymers containing polystyrene and polybutadiene blocks and/or polyisoprene blocks are known. These materials are generally available as pure triblocks, (sometimes referred to as SIS and SBS copolymers), and diblocks (sometimes referred to as SI and SB copolymers). The materials are also available as mixtures of diblock and triblock materials (sometimes referred to as SIS + SI and SIS + SB). Examples of these materials include elastomers marketed by Dexco and by Kraton Polymers.
  • diblock/triblock blends as the elastomeric component in hot-melt pressure-sensitive adhesives. It is further known that adhesive properties and viscosity can be controlled by varying the diblock-to-triblock ratio, varying the styrene content, varying the polymer molecular weight, and varying the block molecular weights within the polymers. Examples of materials that have been used are KRATONTM D 1113, containing 16% styrene and 56% diblock;
  • VECTORTM 4114 containing 42% diblock and 17% styrene
  • VECTORTM 4113 containing 20% diblock and 17% styrene.
  • VECTORTM 4114 and VECTORTM 4113 are Dexco products. While these materials have good adhesive properties when tackified and can be used in label-production hot melts, they lack optimum die-cutting properties. Furthermore, their low temperature adhesive properties are not optimum.
  • US Patent No. 5,663,228 concerns improving label adhesive die-cutability. But the offered solution is complicated, requires two particular block copolymer resins having certain glass-transition temperatures, and requires the choice of a tackifying resin that, when mixed with the two block copolymers, increases the difference between the two block copolymers' glass transition temperatures.
  • styrenic copolymers that are used in the adhesive mixtures of US Patent No 5,663,228 are FINAPRENETM 1205 available from Fina and KRATONTM 1107 available from Kraton Polymers.
  • US Patent No. 5,412,032 concerns linear SIS triblock/diblock copolymers that can improve label die-cutting. This is accomplished using block copolymers with a styrene content from 18-24 wt%, a polystyrene block molecular weight from 25,000-35,000, an overall molecular weight from 280,000-520,000, and a coupling efficiency of 20%-40%. The coupling efficiency corresponds to the triblock percentage in the overall copolymer's triblock content.
  • US Ser. No. 60/214,308 describes adhesive systems with improved die- cutting performance obtained by optimizing a diblock/triblock blend.
  • die-cutting involves relatively low deformation rates and involves pushing the adhesive to the side of the cut line rather than sharply cutting it.
  • the adhesive In successful die cutting, the adhesive must creep when subjected to knife action, flow away from the cut point, and not reform over the cut line.
  • the first aspect may be illustrated by assuming typical conditions of die- cutting operations, i.e. a machine line speed of 100 m/min, a rotating cylinder of 10 cm diameter, and face paper and adhesive layers with a thickness of 80 and 20 microns respectively. Since the diameter of the rotating cylinder is much larger (by a factor 100) than the overall thickness to indent, the effective vertical motion is only 10 cm/s when the knife starts to indent the face paper, and only 2 cm/s when the adhesive itself is indented.
  • Flow or viscoelastic behavior of hot-melt adhesives at a given temperature is conveniently captured by the two dynamic moduli known as G' and G": the loss modulus G" indicating viscous behavior, and the storage modulus G' indicating elastic behavior.
  • the ratio of G" and G' is known as the loss factor Tangent delta (Tan ⁇ ).
  • adhesives with good die-cutting performance usually fulfill the following criteria: G' at room should temperature should decrease monotonically with frequency at frequencies below the glass transition region (typically ⁇ 10 rad/s), down to a constant elastic plateau of storage modulus at the lowest frequencies.
  • the elastic plateau preferably occurs at frequencies lower than 6000 Pa, more preferably lower than 5000 Pa, most preferably lower than 4000 Pa.
  • G' should intersect a value of 10000 Pa at a frequency that is preferably higher than 0.03 rad/s; and more preferably higher than 0.05 rad/s; most preferably higher than 0.1 rad/s.
  • a loss factor Tan ⁇ defined as the ratio G"/G' preferably comprises between 0.4 and 1; more preferably between 0.6 and 1; and most preferably between 0.8 and 1.
  • Figure 1 illustrates a typical die-cutting process.
  • Figure 2 simulates die-cutting: 1 is the paper, 2 is the release coating, 3 is the adhesive layer, 4 is the label stock, and 5 is the die-cutting blade that cuts in an anti-clockwise direction.
  • the simulation shows how, as the knife crushes and breaks through the paper, the adhesive under the cut line is pushed away but does not cut. Accordingly, the more readily the adhesive flows and the less elastic it is the easier and cleaner the cut will be.
  • Figures 3, 4, 5, 6, 7, and 8 provide various plots of frequency vs. G', G", and Tan ⁇ for the examples or comparative examples in this document.
  • the present invention provides an elastomer-or rubber-based, pressure- sensitive adhesive composition, that exhibits excellent convertibility.
  • the adhesive achieves clean adhesive layer rupture when the face stock is cut through.
  • the adhesive provides excellent adhesive properties at ambient and reduced temperatures. It is particularly suitable for use in labels and may be applied as a hot melt. If particular styrenic block copolymer rubbers are used in the label adhesive production, improved die-cutting performance may be accomplished.
  • the present invention therefore provides an adhesive, with a single glass transition temperature, comprising a tackified styrenic block copolymer in which the styrenic block copolymer is diblock, triblock-copolymer mixture containing from 11-23 wt% styrene, preferably 12-20 wt% styrene, and when the diblock material is a styrene/isoprene diblock copolymer, it contains between 58-77 wt % of diblock that has a molecular weight greater than 60,000, alternatively greater than 70,000. And when the diblock material is a styrene/butadiene diblock copolymer, it contains from 40-80 % wt of diblock material that has a molecular weight greater than 50,000, alternatively greater than 65,000.
  • the block copolymers are of styrene (S) and butadiene (B) and/or isoprene (I).
  • the triblock copolymers have the formula SIS and SBS, and the diblock copolymers have the formula SI and SB.
  • the polymer's vinyl aromatic hydrocarbon, generally styrene, content should range from 11-23 wt%, alternatively 12-20 wt%, or 16-18 wt%. These parameters provide a good die cutting and adhesive performance combination.
  • Molecular weights are number average molecular weights and are measured in g/mole by Gel Permeation Chromatography (GPC), where the GPC system has been appropriately calibrated by using standards of similar polymers with known molecular weight.
  • GPC Gel Permeation Chromatography
  • the invention selects rubbers having the structure and rheology combinations that allow the adhesives to be applied as hot melts and that provide good die-cutability when they are used in pressure-sensitive adhesive systems.
  • the rubbers have the following properties: an overall styrene content between 11-23 wt%, alternatively 12-20%; and if the diblock material is a styrene/isoprene (SI) diblock copolymer, a diblock content between 58-77 wt% based on the total block copolymer amount, alternatively 60-75 wt%, or 65-75 wt%, and if the diblock material is a styrene/butadiene (SB) diblock copolymer, a diblock content from 40-80 wt%, alternatively from 50-80 wt%, or more than 60- 80 wt%.
  • SI styrene/isoprene
  • SB styrene/butad
  • diblock copolymers can contain from 16-20 wt% styrene.
  • diblock contents lower than 77 wt% are desirable because when such levels are used in hot melt adhesives the storage modulus G' remains at or below the loss modulus G" in the low frequency regime.
  • This predominance of elastic behavior over elastic behavior solves a number of critical problems in self-adhesive label applications.
  • the holding power performance is suitable and there is a lesser cohesive failure possibility long times low loadings. Also, this prevents the 'cold flow' tendency that creates storage difficulties, the so-called ousing phenomenon.
  • the styrenic block copolymers with a molecular weight from 45,000-250,000 g/mole.
  • the styrenic blocks have a molecular weight from 4000-35,000 g/mole.
  • Styrenic block molecular weights of 4000 g/mole or above typically provide suitable holding power, shear properties, and cohesive strength.
  • Molecular weights less than 35,000 g/mole give a sufficiently pliable adhesive that has suitable pressure sensitivity.
  • the unsaturated diene blocks should have a molecular weight of from
  • Unsaturated diene blocks of molecular weight 20,000 g/mole or greater provide a suitably strong polymer with good shear properties. Unsaturated diene blocks of molecular weight 200,000 g/mole or less process appropriately. Some embodiments select styrene/isoprene block polymers, in which the triblock material molecular weight, particularly SIS triblocks, is between 45,000- 300,000 g/mole, alternatively between 100,000-180,000 g/mole, or 100,000- 150,000 g/mole.
  • diblock material molecular weight particularly SI diblocks between 60,000-150,000 g/mole, alternatively between 70,000-140,000 g/mole, or between 80,000-110,000 g/mole.
  • the diblock material is a styrene/butadiene diblock
  • a material molecular weight between 50,000-150,000 g/mole, alternatively 65,000-110,000 g/mole, or 70,000-90,000 g/mole is selected.
  • Molecular weight means peak molecular weight as measured by polystyrene calibrated Gel Permeation Chromatography (sometimes known as size exclusion chromatography). Commercially available polystyrene standards were used for calibration, and the copolymer molecular weights were corrected according to Runyon et al, J. Applied Polymer Science. Vol. 13 Page 359 (1969) and Tung, L H J. Applied Polymer Science. Vol. 24 Page 953 (1979).
  • Chromatography used a Hewlett-Packard Model 1090 chromatograph equipped with a 1047A refractive index detector and four 300 mm x 7.5 mm Polymer Laboratories SEC columns packed with five micron particles. Of the five columns, two columns had 10 5 angstrom pore size, one had 10 4 angstrom pore size, and one had mixed pore sizes.
  • the carrier solvent was HPLC grade tetrahydrofuran (THF) with a flow of 1 ml/min. Column and detector temperatures were 40°C, and run time was 45 minutes. The following rheological properties are also important in these polymer systems.
  • G' should monotonically decrease with frequency at frequencies below the T g region, down to a constant elastic plateau of storage modulus at the lowest frequencies preferably lower than 6000 Pa. G' should become lower than 10 000 Pa at frequencies as high as possible, preferably higher than 0.01 rad/s.
  • the loss factor for Tan ⁇ is preferably between 0.2 and 1 at this frequency.
  • Inventive adhesive tackifier additives are chosen based on the particular rubber that is used. But most tackifiers may be used. Preferred tackifiers are resins from aliphatic petroleum derivative streams containing 5-or-6-carbon-atom dienes and mono-olefins. The tackifiers range from materials that are normally liquid at room temperature to those that are normally solid at room temperature.
  • the resins typically contain 40 weight percent or more of polymerized dienes.
  • the dienes are typically piperylene and/or isoprene.
  • Useful tackifiers include ESCOREZTM 1310 LC manufactured by Exxon Mobil Chemical softening point 91°C, PICCOTACTM 95 manufactured by Hercules, and the WTNGTACKTM resin family manufactured by Goodyear (with the numerical designation being the softening point) such as WTNGTACKTM 95, which is a solid resin having a softening point of about 95 °C, and WTNGTACKTM 10, which is a liquid resin having a softening point of about 10°C.
  • Suitable tackifiers include hydrogenated or non-hydrogenated resins, such as aromatic/aliphatic resins.
  • ExxonMobil Chemical is a typical tackifier.
  • Hydrogenated polycyclic resins typically dicyclopentadiene resins such as ESCOREZTM 5300, 5320, 5340, and 5380 manufactured by ExxonMobil Chemical
  • Hydrogenated, polycyclic aromatic modified resins such as ESCOREZTM 5690, 5600, and 5620, manufactured by ExxonMobil Chemical, may also be used.
  • Hydrogenated aromatic resins in which a substantial portion, if not all, of the benzene rings are converted to cyclohexane rings may also be used.
  • REGALREZTM family of resins manufactured by Hercules such as REGALREZTM 1018, 1033, 1065, 1078, and 1126 and REGALITETM R-100
  • ARKONTM family of resins from Arakawa Chemical such as ARKONTM P-85, P-100, P-115 and P-125
  • ARKONTM P-85, P-100, P-115 and P-125 may also be used.
  • Rosin esters, polyterpenes, and other tackifiers which are compatible with the polyisoprene and polybutadiene phases and to some degree with the polystyrene end blocks, can also be added.
  • Other additives include plasticizer oils such as SHELLFLEXTM 371, manufactured by Shell, and KAYDOLTM mineral oil, manufactured by Witco, which are soluble in both the polyisoprene and polybutadiene phases.
  • the tackifier may be present from 50% by weight, alternatively 60%, based on the total weight of tackifier and copolymers. It may be present at up to 80% by weight, alternatively up to 70% by weight. Conversely, the block copolymers are present from 20%, alternatively 30%, by weight based on the weight of the tackifier and the copolymers and up to 50%, alternatively to 45 %, by weight based on the weight of the tackifier and the copolymers.
  • the resin additive is preferably a mixture of a normally solid tackifier such as ESCOREZTM 1310 LC and a normally liquid tackifier such as WTNGTACKTM 10 or a plasticizer oil such as SHELLFLEXTM 371.
  • Tackifiers also known as hydrocarbon or petroleum resins
  • hydrocarbon or petroleum resins are well known and are generally produced by Friedel-Crafts or thermal polymerization of various feeds, which may be pure monomer feeds or refinery streams containing mixtures of various unsaturated materials.
  • the purer the feed the easier the polymerization.
  • pure styrene, pure ⁇ -methyl styrene and these mixtures are easier to polymerize than a C 8 /Cg refinery stream.
  • pure or concentrated piperylene is easier to polymerize than C to C 6 refinery streams. But these pure monomers are more expensive to produce than the refinery streams, which are often large volume refining byproducts.
  • Aliphatic hydrocarbon resins can be prepared by cationic polymerization of a cracked petroleum feed containing C 4 , C 5 , and C 6 paraffins, olefins, and diolefins also referred to as "C 5 monomers". These monomer streams are comprised of cationially polymerizable monomers such as butadiene, 1,3- pentadiene (piperylene) along with cyclopentene, pentene, 2-methyl-2-butene, 2- methyl-2-pentene, isoprene, cyclopentadiene, and dicyclopentadiene.
  • the refining streams are purified usually by fractionation and impurity removal to obtain these feeds.
  • Non-polymerizable components in the feed include saturated hydrocarbons, which can be co-distilled with the unsaturated components such as pentane, cyclopentane, or 2-methylpentane. This monomer feed can be co-polymerized with other C 4 or C 5 olefins or dimers.
  • the feed should be purified (typically by fractionation) to remove unsaturated materials that adversely affect the polymerization reaction or give undesirable color to the final resin (for example isoprene).
  • C 5 aliphatic hydrocarbon resins are synthesized using a piperylene concentrate stream that is fractionation-enriched to increase the piperylene content and to reduce the difficult-to-polymerize olefin and diolefin content.
  • the feedstream includes at least 20 wt %, alternatively 30 wt %, or 50 wt %, monomer and up to 80 wt %, alternatively 70 wt %, or 30 wt %, solvent.
  • the solvent may be aromatic or aliphatic.
  • the solvent may be a non-polymerizable feed component.
  • the feedstream may include at least C 4 -C 6 monomers, from which cyclopentadiene and methylcyclopentadiene components may be removed by heating between 100°C and 160°C and fractionally distilling.
  • the monomers may include at least one of isobutylene, butadiene, 2-methyl-2-butene, 1-pentene, 2- methyl-1-pentene, 2-methyl-2-pentene, 2-pentene, cyclopentene, isoprene, cyclohexene, 1,3-pentadiene, 1,4-pentadiene, isoprene, 1,3-hexadiene, 1,4- hexadiene, cyclopentadiene, and dicyclopentadiene.
  • the feedstream can include at least 30 wt %, alternatively 50 wt %, of C 5 monomers, as described above and at least 5 wt %, alternatively 15 wt % of a co-feed including at least one of pure monomer, C 9 monomers, and terpenes.
  • the feedstream can include up to 95 wt %, alternatively up to 85 wt % of C 5 monomers, as described above and up to 70 wt %, alternatively up to 50 wt %, of a co-feed including at least one of pure monomer, C 9 monomers, and terpenes.
  • the feed may also contain aromatic olefins such as styrene, indene, ⁇ - methylstyrene, ⁇ -methylstyrene, indene, substituted indenes, such as methylindenes, vinyl toluenes, and their derivatives.
  • aromatic olefins are typically present at levels of at least 1 wt %, and at levels up to 50 wt %, alternatively up to 30 wt %, or 10 wt %.
  • Polymerization may be by continuous or batch processes.
  • a batch process reaction time is usually at least 30 minutes, alternatively 60 minutes, and no greater than 8 hours, alternatively 4 hours.
  • Polymerization may be stopped by removing the catalyst from the hydrocarbon resin, for example, by filtration.
  • the hydrocarbon resin may be removed from a fixed bed reactor, which includes the catalyst.
  • Polymerization temperatures are at least -50°C to 150°C, alternatively -20°C to 100 ° C. Reaction temperature significantly affects resin properties. Higher-molecular-weight and high-softening-point resins are prepared at lower reaction temperatures.
  • the hydrocarbon resin may be stripped to remove unreacted monomers, solvents, and low-molecular-weight oligomers. These unreacted monomers, solvents, and low-molecular-weight oligomers may be recycled.
  • the monomer feed can be co-polymerized with C 4 or C 5 olefin or dimers as chain transfer agents.
  • Chain transfer agents Up to 40 wt %, alternatively up to 20 wt %, of chain transfer agents may be added to obtain resins with lower molecular weight and narrower molecular weight distributions than can be prepared using monomers alone.
  • Chain transfer agents terminate polymer chain growth such that polymer initiation sites regenerate.
  • Components that behave as chain transfer agents in these reactions include but are not limited to isobutylene, 2-methyl-l-butene, 2- methyl-2-butene, or dimers or oligomers of these species.
  • the chain transfer agent can be added to the reaction in pure form or diluted in a solvent.
  • aromatic solvents are used, such as toluene, xylenes, or light aromatic petroleum solvents. These solvents can be used fresh or recycled from the process.
  • the solvents generally contain less than 200 ppm water, alternatively less than 100, or less than 50 ppm water.
  • the resulting resin has a number average molecular weight (Mn) of at least 400, a weight average molecular weight (Mw) of at least 500, a Z average molecular weight (Mz) of at least 700, and a polydispersity (PD) as measured by Mw/Mn of at least 1.5 where Mn, Mw, and Mz are determined by Gel Permeation chromatography.
  • the resin has a number average molecular weight (Mn) up to 2000, a weight average molecular weight (Mw) of up to 3500, a Z average molecular weight (Mz) of up to 15,000 and a polydispersity (PD) as measured by Mw/Mn up to 4.
  • Mn number average molecular weight
  • Mw weight average molecular weight
  • Mz Z average molecular weight
  • PD polydispersity
  • the hydrogenation may be carried out via molten-resin' or resin-solution-based processes by either batchwise or, more commonly, continuous processes.
  • Supported monometallic and bimetallic catalysts based on Group-6, -8, -9, -10 or -11 elements are typically used for hydrocarbon resin hydrogenation.
  • Catalysts such as supported nickel (for example, nickel on alumina, nickel on charcoal, nickel on silica, nickel on kieselguhr, etc), supported palladium (for example, palladium on silica, palladium on charcoal, palladium on magnesium oxide, etc) and supported copper and/or zinc (for example copper chromite on copper and/or manganese oxide, copper and zinc on alumina, etc) are good hydrogenation catalysts.
  • the support material typically consists of porous inorganic refractory oxides such as silica, magnesia, silica-magnesia, zirconia, silica-zirconia, titania, silica-titania, alumina, silica- alumina, alumina-silicate, etc, with supports containing ⁇ -alumina being highly preferred.
  • the supports are essentially free of crystalline molecular sieve materials. Mixtures of the foregoing oxides are also contemplated, especially homogeneous mixtures.
  • the useful support materials in the present invention are the supports disclosed in the US Patent Nos. 4,686,030, 4,846,961, 4,500,424, and 4,849,093.
  • Some embodiments select alumina, silica, carbon, MgO, TiO 2 , ZrO 2 , FeO 3 or their mixtures as supports. Any of the known processes for catalytically hydrogenating hydrocarbon resins can be used, particularly the processes of US 5,171,793, US 4,629,766, US 5,502,104 and US 4,328,090 and WO 95/12623.
  • Generic hydrogenation conditions include reaction temperatures of 100°C - 350°C and hydrogen pressures of 5 atmospheres (506 kPa)-300 atmospheres (30390 kPa), for example, 10 to 275 arm. (1013 kPa to 27579 kPa). Some embodiments select hydrogenation temperature in the range 180 °C to 320 °C.
  • pressure of 15195 kPa to 20260 kPa hydrogen.
  • the hydrogen-to-feed volume ratio to the reactor under standard conditions typically can range from 20-200.
  • 100- 200 is selected for the production of water- white resins.
  • Some embodiments select catalysts comprising nickel and/or cobalt on one or more of molybdenum, tungsten, alumina, or silica supports. These or other embodiments select 2 to 10 wt% of nickel oxide and/or cobalt oxide on the support. After preparation, the support contains 5 - 25 wt% tungsten or molybdenum oxide. Alternatively, the catalyst contains 4 - 7 wt % nickel oxide and 18 - 22 wt % tungsten oxide.
  • pressure-sensitive invention adhesive formulations exhibit excellent low and ambient temperature performance, as well as good die cutting performance, they may also enhance elevated-temperature performance. This may be accomplished by cross-linking such as with electron beam (EB) and ultraviolet (UV) radiation and chemical cross-linking techniques. If employed, tackifying additives should be substantially saturated so that all of the cure energy goes into cross-linking the adhesives' elastomeric components.
  • EB electron beam
  • UV ultraviolet
  • the adhesive formulations may also contain well-known additives such as anti-block, anti-static, antioxidants, UV stabilizers, neutralizers, lubricants, surfactants and/or nucleating agents.
  • additives such as anti-block, anti-static, antioxidants, UV stabilizers, neutralizers, lubricants, surfactants and/or nucleating agents.
  • These can include silicon dioxide, titanium dioxide, polydimethylsiloxane, talc, dyes, wax, calcium stearate, calcium carbonate, carbon black, and glass beads.
  • Invention adhesives may be used as pressure-sensitive, hot-melt or contact adhesives and used in applications such as tapes, labels, paper impregnation, hot- melt adhesives, including woodworking, packaging, bookbinding or disposables, sealants, rubber compounds, pipe wrapping, carpet backing, contact adhesives, road-marking or tire construction. They are particularly useful as hot-melt pressure-sensitive adhesives used for tapes and labels where they impart improved die-cutting performance.
  • Hot-melt pressure-sensitive adhesives were prepared by mixing the block copolymers with the tackifying resins in a 300 ml laboratory z blade mixer, at
  • the pressure sensitive adhesives were applied to a silicone coater paper at a coating weight of about 20 g/m , using an Acumeter laboratory coater with a slot die for the molten adhesive formulation at 165 °C. Lamination was done according to industry practice by transfer coating from a silicone coater paper
  • Migration was evaluated by comparing the whiteness of the paper frontal substrate after ageing at 60 and 70 °C for one and two weeks. Whiteness was evaluated with a Hunterlab spectrophotometer.
  • Dynamic rheological properties at 20°C were determined on RDAII and SR-500 instruments manufactured by Rheometric Scientific, Piscataway, New Jersey. The former gives access to frequencies between 10 "2 to 100 rad.s "1 and temperatures lower than 20°C (down to -70°C) to reach the glassy region obtained at higher frequencies.
  • the SR-500 instrument which covers a frequency range between 10 "5 to 100 rad.s "1 at room temperature was used for the terminal zone (lower frequencies).
  • Frequency sweeps were carried out at deformation levels well within the linear viscoelastic region. To broaden the accessible experimental frequencies range, time-temperature superposition was applied with care. Measurements in frequencies from IE - 04 to IE + 02 were made at 20°C whereas at higher frequencies, lower temperatures were used, and the measurements were extrapolated to 20°C. This was done because phase-structure changes may occur at high temperature.
  • samples were degassed overnight under primary vacuum at about 90°C. Disks of adequate diameter were then compression molded, at a temperature systematically lower than the mixing temperature (145°C).
  • a hot melt formulation was prepared with 31 wt% of a pure triblock copolymer 27 wt% of WTNGTACKTM 10, and 42 wt% of ESCOREZTM 1310.
  • 29 wt% of a SIS triblock with a molecular weight of 130 000 g/mole and a styrene content of 17 wt% and 71 wt% of a SI diblock with a molecular weight of 89 000 g/mole and a styrene content of 16.1 wt% were mixed to make an SIS/SI polymer blend.
  • a hot melt formulation was prepared with 31 % of the blend, 27 wt% of WTNGTACKTM 10, and 42 wt% of ESCOREZTM 1310 and 0.4 % IRGANOXTM 1076.
  • SIS/SI polymer blend 25 wt%> of a SIS triblock with a molecular weight of 129 000 g/mole and a styrene content of 16.5 wt% and 75 wt% of a SI diblock with a weight-average molecular weight of 106 000 g/mole and a styrene content of 16.6 wt% were mixed to form an SIS/SI polymer blend.
  • a hot melt formulation was prepared with 43 wt% of the blend, 17 wt% of WTNGTACKTM 10, 40 wt% of ESCOREZTM 1310 and 0.4 wt% IRGANOXTM 1076. In this case, the use of less liquid resin (WTNGTACKTM 10) reduces resin migration through the face paper.
  • the resulting hot melt showed the following characteristics.
  • the adhesives' dynamic rheological properties are compared with those of Comparative Examples 1 and 2 in Figure 5. Note that the plateau modulus at low frequencies is 4 000 Pa, lower than for both Comparative Examples. G' intersects a value of 10 000 Pa at a frequency of 0.05 rad s, where Tan ⁇ equals 0.8. These valves indicate that adhesives with this polymer blend will enhance die cutting.
  • a hot melt formulation was prepared with 31 wt% of the blend, 27 wt% of WTNGTACKTM 10, 21 wt% of ESCOREZTM 1310 and 21 wt% of ECRTM-373 and 0.3 wt% IRGANOXTM 1076. The resulting hot melt showed the following characteristics.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des adhésifs d'étiquette améliorés, composés de mélanges déterminés de copolymères blocs styrènes di- et tri-, présentant un comportement élastique réduit en découpage à la presse.
EP01950605A 2000-06-27 2001-06-26 Adhesifs a performance amelioree en decoupage a la presse Expired - Lifetime EP1299495B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08000424A EP1905808B1 (fr) 2000-06-27 2001-06-26 Adhésifs stables présentant une performance améliorée de découpage à l'emporte-pièce

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US21430800P 2000-06-27 2000-06-27
US214308P 2000-06-27
PCT/US2001/020609 WO2002000805A2 (fr) 2000-06-27 2001-06-26 Adhesifs a performance amelioree en decoupage a la presse

Related Child Applications (1)

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EP08000424A Division EP1905808B1 (fr) 2000-06-27 2001-06-26 Adhésifs stables présentant une performance améliorée de découpage à l'emporte-pièce

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EP1299495B1 EP1299495B1 (fr) 2008-01-16

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CN1478134A (zh) 2004-02-25
BR0112046A (pt) 2004-06-29
AU2001271577A1 (en) 2002-01-08
JP5442175B2 (ja) 2014-03-12
JP2004518770A (ja) 2004-06-24
DE60132457T2 (de) 2009-01-22
US20040007322A1 (en) 2004-01-15
WO2002000805A3 (fr) 2002-05-23
MXPA03000181A (es) 2004-09-13
WO2002000805A2 (fr) 2002-01-03
BR0112046B1 (pt) 2011-11-16
CN1213123C (zh) 2005-08-03
KR100774783B1 (ko) 2007-11-07
KR20040030177A (ko) 2004-04-09
DE60132457D1 (fr) 2008-03-06
EP1299495B1 (fr) 2008-01-16
MY143123A (en) 2011-03-15

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